Acid dyestuffs of the anthraquinone series



Patented Mar. 10, 1936 UNITED STATES PATENT OFFICE ACID DYESTUFFS OF THEANTHRA- QUINONE SERIES tion of Delaware No Drawing. Application May 9,1935, Serial No. 20,705. In Germany May 19, 1934 Claims.

The present invention relates to acid wool-dyestuffs of theanthraquinone series.

We have found that new dyestuffs of good fastness properties areobtainable by causing an am- 5 inoaralkyl-alkyl-sulfone, for instance,of the following formula:

X means a sulfo group or a salt thereof, R1 an aryl radical of thebenzene series, R2 a methylene or ethylene group and 4 R3 an alkylradical.

They are distinguished by a very good levelling power. It could not beexpected that the sulfone group in the dyestuff molecule would bringabout this levelling effect since it is not directly linked to the arylnucleus. Considering that the simplest components used for thepreparation of the present dyestuffs constitute side-chain substitutionproducts of toluidines it is surprising that the new dyestuffs yielddyeings of a considerably enhanced evenness as compared with thoseobtainable with the corresponding toluidine dyestuffs.

According to the present invention there may be obtained, for instance,from l-amino-l-bromanthraquinone-Z-sulfonic acid by reaction with 5ortho-amino-benzyl-methyl-sulfone a dyestuff which yields on wool veryvivid reddish blue tints and which, as regards its levelling power,surpasses the best commercial dyestuff of this shade. The presentprocess, therefore, constitutes an in- 10 dustrial progress.

The following examples serve to illustrate the invention, but they arenot intended to limit it thereto, the parts being by weight:

(1) 40 parts of l-aminol-bromanthraquin- 15 one-2-sodium sulfonate areheated for several hours at C.- C. with 26 parts oforthoaminobenzylmethylsulfone of the formula:

CHE-S Oz-CHa in 180 parts of water in the presence of 4 parts of sodiumcarbonate, 20 parts of sodium bicarbonate' and 1 part of cuprouschloride until the 25 formation of the dyestufi is finished. On cooling,the sodium salt of the dyestuff separates in the form of coarsecrystals. It is filtered with suction and washed with dilute sodiumchloride solution. In the dry state, the dyestufi forms a blue powderwhich dyes wool from an acid bath clear reddish blue tints of very goodevenness. It has the following constitution:

Ol NH2 SOaH Ortho-aminobenzyl-methylsulfone used for the condensationmay be prepared as follows: 34 45 parts of ortho-nitrobenzylchloride areheated to boiling for several hours with 25 parts of methansodiumsulfinate in parts of methanol. After cooling, the crystalline magma isfiltered with suction and washed free from sodium chloride 50 by meansof water. Ortho-nitrobenzyl-methylsulfone melts at 121 C. By reduction,orthoaminobenzyl-methylsulfone is obtained which melts at 117 C.-118 C.

(2) By replacing in Example 1, 26 parts of.

O NHi s 03H The meta-aminobenzyl-methylsulfone used for the condensationmay be obtained from metanitrobenzylchloride as described in Example 1.Meta-nitrobenzyl-methylsulfone melts at 121 C.Meta-aminobenzyl-methylsulfone melts at 126 C.

(3) 40 parts of l-amino-4-bromanthraquinone- 2-sodium sulfonate areheated to gentle boiling with 24 parts of para-aminobenzyl-methylsulfonein 140 parts of water and 100 parts of alcohol in the presence of 4parts of sodium carbonate, 20 parts of sodium bicarbonate and 1 part ofcuprous chloride until the formation of the dyestuff is finished. Thedyestufi may be purified in the usual manner. In the dry state it formsa blue powder which dyes wool from an acid batlr clear blue tints.

The para aminobenzyl methylsulfone used may be prepared frompara-nitrobenzylchloride in the manner described in Example 1.Paranitrobenzyl-methylsulfone melts at 171 C.-172 0., para aminobenzylmethylsulfone melts at 170 C.

(4) By replacing in Example 1, 26 parts ofortho-aminobenzyl-methylsulfone by 30 parts ofortho-aminobenzyl-ethylsulfone and carrying out the condensation at C.to C. as indicated in this example, a blue dyestuff is obtained whichdyes wool clear reddish blue tints.

The ortho-aminobenzyl-ethylsulfone used for the condensation may beobtained in the following manner: A mixture of 34 parts oforthonitrobenzylchloride, 28 parts of the sodium salt of ethane-sulfinicacid and 150 parts of methanol is heated to boiling for several hours.The crystalline magma is filtered by suction and washed free from sodiumchloride by means of water. The ortho-nitrobenzyl-ethylsulfone melts at84 C. to 85 C., the ortho-aminobenzyl-ethylsulfone melts at 113 C.

By using instead of ortho-aminobenzyl-ethylsulfone the correspondingcompound in which the ethyl group is replaced by another alkyl group as,for instance, propyl,a similar dyestuff is obtained.

' (5) A dyestufi of similar properties is obtained by replacing inExample 1, 26 parts of orthoaminobenzyl-methylsulfone by 30 parts ofmetaaminobenzyl-ethylsulfone melting at C. The dyestuff dyes wool froman acid bath clear blue tintsof good evenness.

(6) By using in Example 1 for the condensation instead of 26 parts ofortho-aminobenzylmethylsulfone, 30 parts ofpara-aminobenzylethylsulfone, a blue dyestufi is obtained which dyeswool clear blue tints.

The para-aminobenzyl-ethylsulfone used for the condensation may beprepared from paranitrobenzylchloride in the manner described in Example4. Para-nitrobenzyl-ethylsulfone melts at 133 C. to 134 C.,para-aminobenzyl-ethylsulfone melts at 113 C. to 115 C.

(7) A mixture of 40 parts of the sodium salt of 1 amino 4bromoanthraquinone-2-sulfonic acid, 28 parts ofl-(methylsulfonyl)-2-(4'-aminophenyl) -ethane, parts of water, 4 partsof sodium carbonate, 20 parts of sodium bicarbonate and 1 part ofcuprous chloride is heated at 70 C. to 85 C. for several hours, untilthe formation of dyestufi is finished. The product is worked up in theusual manner. A blue dyestufi is obtained which dyes wool from an acidbath clear greenish blue tints.

A similar dyestufi is obtained by using for the reaction instead of 28parts of l-(methylsulfonyl)-2-(4-aminophenyl) ethane, 28 parts of 1-(ethylsulfonyl) -2- (4-aminophenyl) ethane.

The 1- (methylsulfonyl) -2- (4-aminophenyl) ethane used may be preparedfrom 1-bromo-2- (4'-nitrophenyl) -ethane in the manner described.

in Example 1. l-(methylsulfonyl) -2-(4'-nitrophenyl)-ethane melts at 142C..143 C.; 1- (methylsulfonyl) 2 (4' aminophenyl) -ethane melts at 98C.-99 C.; 1-(ethylsulfonyl)-2-(4'- nitrophenyl) -ethane melts at 65 C.;l-(ethylsulfonyl)-2-(4'-aminophenyl)-ethane melts at 86 C.-87 C.

(8) A mixture of 40 parts of the sodium salt of l-amino 4bromanthraquinone 2 sulfonic acid, 28 parts of3-amino-4-methoxybenzylmethyl-sulfone, 200 parts of water, 4 parts ofsodium carbonate, 20 parts of sodium bicarbonate and 1 part of cuprouschloride is heated for 4 to 5 hours at 65 C. to 80 C. The sodium salt ofthe dyestufi which has separated in the form of coarse blue greencrystals is filtered by suction and washed with dilute sodium chloridesolution. In the dry state, the dyestuff forms a blue powder which dyeswool from an acid bath clear blue tints of good evenness. V

The 3-amino 4 methoxybenzylmethylsulfone used for the condensation maybe prepared from 3-nitro-4-methoxybenzylchloride in the manner describedin Example 1. 3-nitro-4-methoxybenzyl-methylsulfone melts at 158 C.-159C., 3- amino-4-methoxybenzyl-methylsulfone melts at 90 C.-91 C.

(9) By replacing in Example 8, 28 parts of 3 amino 4methoxy-benzylmethylsulfone by 28 parts of3-amino-6-methoxybenzyl-ethylsulfone and carrying out the condensationat 70 C.-75 C., a dyestuff is obtained which dyes wool from an acid bathclear blue tints.

The 3 amino 6 methoxybenzylethylsulfone used for the condensation may beprepared from 3-nitro-6-methoxybenzylchloride in the manner described inExample 4. 3-nitro-6-methoxy-benzylethylsulfone melts at 139 C.-140 C.,3-amino- 6-methoxybenzylethylsulfone melts at 143 C.

(10) By replacing in Example 8, 28 parts of 3- amino 4methoxybenzylmethylsulfone by 28 parts of3-amino-6-methoxy-benzylmethylsulfone and heating for several hours at70 C. to 85 C., a blue dyestufi is obtained which dyes wool from an acidbath clear greenish blue tints of good evenness. It has the followingconstitution:

fi NH:

-SO:H

( HN- OCH:

CHFS Oz-CH:

The 3-amino-6-methoxybenzylmethylsulfone used for the condensation maybe prepared from 3-nitro-6-methoxybenzylchloride in the manner describedin Example 1. 3-nitro-6-methoxybenzylmethylsulfone melts at 110 C.-1110., 3- amino-6-methoxybenzylmethylsulfone melts at 102 C.-103 C.

We claim:

1. The compounds of the general formula:

(I) IIJHz A HNR1R2-SOz'Ra wherein X means a sulfo group or a saltthereof, R1 an aryl radical of the benzene series, R2 a methylene orethylene group and R3 an alkyl radical, said compounds being aciddyestufis dyeing wool clear blue tints.

2. The compounds of the general formula:

II I

SOzONa O HNR CHzSOz-Rx wherein R1 means an aryl radical of the benzeneseries, and R3 methyl or ethyl, said compounds being acid dyestuffsdyeing wool clear blue tints.

3. The compound of the formula:

being a blue powder which dyes wool from an acid bath clear reddish bluetints of very good evenness.

4. The compound of the formula:

(? NHI -SO|ONa Q o HN-- ]HiSO -OH;

being a blue dyestuif which dyes wool from an acid bath clear bluetints.

5. The compound of the formula:

SO2ON8 HN- OCH:

CIEh-SOr-CH;

being a blue dyestuff which dyes wool from an acid bath clear greenishblue tints of good evenness.

KARL ZAHN. HEINRICH KOCH.

